Sulfopropylated, organofunctional silanes and siloxanes



United States Patent 3,328,449 SULFQPROPYLATED, GRGANOFUNCTIGNAL SILANES AND SILOXANES Loren A. Haluslra, Midland, Mich, assignor to Dow Corning Corporation, Midland, Mich, a corporation of Michigan No Drawing. Fiied Dec. 5, 1963, Ser. No. 328,164 8 lairns. (Cl. 260-4482) This application relates to new, sultopropylated, organofunctional silanes and siloxanes that are useful as detergents, ion exchange resins, wetting agents, antistat agents for synthetic fibres, and polymerization catalysts, for siloxanes.

The compositions of this invention are of the formula Z Si[-R(Y[R'SO M where R is a divalent or trivalent hydrocarbon, halohydrocarbon, or hydrocarbon ether radical, there being no more than two Y groups on any one carbon atom.

Where each R" is independently selected from hydrogen or aliphatic hydrocarbon radicals from 1 through 6 carbon atoms, Q is an alkylene radical of 2 through 4 carbon atoms that separates the two N groups by at least two carbon atoms, d is an integer of 0 or 1, R is an alkylene radical that separates Y and S0 by three carbon atoms, M consists of hydrogen, the ammonium radical, or metal atoms, 0 is an integer of 1 through 3; b is an integer of 1 through 2, a is an integer of 1 through 2, and f is the reciprocal of the valence of M. Z consists of hydrogen atoms or monovaleut hydrocarbon, alkoxy, beta-alkoxyalkoxy, phenoxy, acyloxy, or hydrocarbyl-substituted isocyanoxy radicals, and e is an integer of 2 or 3, the sum of e and a being 4.

The compositoins of this invenion can also consist of a siloxane with at least one unit of the formula (4ae) 2 where e is an integer of 0 through 2, and the other symbols are as defined above; any other units in the siloxane being of the formula A SiO where g is an integer with a value of 0 through 3, and A consists of hydrogen, monovaleut hydrocarbon or halohydrocarbon radicals, alkoxy, beta-alkoxyalkoxy, acyloxy, phenoxy, hydrocarbyl-substituted isocyanoxy, or hydroXy radicals.

R can consist of any divalent hydrocarbon radical such as methylene, octadecylene, isobutylene, allylene, butadiylene, cyclohexylene, phenylene, tolylene, l-phenylethylene; and divalent halohydrocarbon radical such as chlorobutylene, decafluorooctadecylene, 3-bromopropylene, 3- chloroallylene, tetrafiuorophenylene; and any divalent hydrocarbon ether such as 3,323,449 Patented June 27, 1967 ice R can also be any trivalent hydrocarbon radical such as CH CH=CHCH2 CH2(|)H(}H2 CHP any trivalent halohydrocarbon radicals such as 01H 0 Fr- CF2- CaHioCls- 01H 0111 or any trivalent hydrocarbon ether such as oH, CI{ZOOH/ -CHOC8H15,

OHzo CaHmi S R" can be hydrogen or any monovaleut aliphatic hydrocarbon radical of 1 through 6 carbon atoms such as methyl, isopropyl, hexyl, cyclohexyl, etc.

Q can be any divalent alkylene radical of 2 through 4 carbon atoms, that separated the two N groups by at least 2 carbon atoms, such as ethylene, propylene, butylene, isopropylene, etc.

R can be any alkylene radical that separates Y and S by three carbon atoms such as propylene, isobutylene, 2-ethylpr-opylene, 1,2,3-trimethylpropylene, 2,2-dimethylpropylene, and

CisHtn -CHzOHCH2- M can be hydrogen, the ammonium radical, or any metal atom such as sodium, potassium, calcium, magnesium, aluminum, iron (ferric or ferrous), manganese, copper, etc.

Z can be a hydrogen atom; any monovalent hydrocarbon or halohydrocarbon radical such as methyl, chloromethyl, octadecyl, decabromooctadecyl, 3,3,3-trifluoropropyl, vinyl, cyclohexyl, perchlorocyclohexyl, phenyl, iodophenyl, tolyl, isobutyl, etc.; any alkoxy radical such as methoxy, isopropoxy, decoxy, ethoxy, etc.; any betaalkoxyalkoxy radical such as CH OCH CH O,

etc.; any acyloxy radical such as acetate, propionate, isopropionate, isobutyrate, decanoate, etc.; phenoxy; any hydrocarbyl-substituted isocyanoxy such as A can be a hydrogen atom; any monovalent hydrocarbon or halohydrocarbon radical such as methyl, chloromethyl, octadecyl, decabromooctadecyl, 3,3,3-trifiuoropropyl, vinyl cyclohexyl, perchlorocyclohexyl, phenyl, iodophenyl, tolyl, isobutyl, etc.; any alkoxy radical such as methoxy, isopropoxy, decoxy, ethoxy, etc.; any betaalkoxyalkoxy radical such as CH OCH CH O-, C H OCH CH O,

fi l3OOHCH20 etc.; any acyloxy radical such as acetate, propionate, isopropion'ate, isobutyrate, decanoate, etc.; phenoxy; any ketoxime radical such as (CH C=NO,

and hydroxy radicals.

Infrared studies indicate that when Y is an amino group,

internal and polymeric salts can be formed between the amino and sulfonate groups.

The compositions of this invention can be made by reacting a propane sultone of the formula OQa-CQ:

/o Q2- a with compounds of the formula Z Si[R(YM or with siloxane-containing units of the formula IG 0 M1=) bis where h is the valence of Y'divided by the valence of M, each Qis a hydrogen atom or an alkyl radical, and the other symbols are identified above with respect to the formulae above.

It should noted that h can be fractional, i.e., that there may be more than one Y group per M group. For example, if Y is COO (monovalent) and M is calcium VSiOHzCHzPDONav we can see that a equals 1, 1) equals 1, h equals 1/1 or 1, and 1 equals 1/1. Therefore, abh/f equals 1, i.e., one mole of sultone reacts with one mole of silyl group.

However, if we use (EHQCIIZSOQ VSiCHaCH l CHgCHzSQa instead of the above silyl compound, then a equals 1, b equals 2, h equals l/ 2, and 1 equals 1/2; abh/f, therefore, equals 2, meaning that two moles of sultone can react with one mole of silyl group.

h and f are included in the .expression abh/f to account for the case where Y and M are of unequal valence. For

example, if we replace the above silyl compound with VS (OH2OH2C ITTC 2C 2 2)z then a equals 2, b equals 1, h equals 3/1, and 1 equals 1/1; abh/f, therefore, equals 6; i.e., up to six moles of sultone will react with each mole of the above silyl compound.

This reaction can be run anywhere in the range of about 20 to C. A common solvent such as methanol or benzene is added to the reaction mixture along with the reactants. Heating of the reaction mixture should be with caution, for some of the reactions are exothermic, e.g. reactions where the primary amine is involved.

If the product is not an insolube salt, as many of the a metal salts are, an alkaline catalyst will often push the equilibrium of the reaction toward the product end, enhancing the yield.

The reactants can all be prepared by wellknown processes; many of them are sold commercially.

The sultones shown above can be prepared by reacting sodium bisulfite with a compound of the following formula:

where Q is defined above. The reaction is as follows:

CQ'zSOz Numerous other methods for preparing sultones are known to the art. For example, German Patent 1,107,220 discloses the method of heating gamma or delta-halosulfonic acid salts of sodium or ammonium in a vacuum, to obtain a sultone plus the halide. of sodium or ammonium. German Patent 902,615 discloses the method of making sultones from aliphatic ether monosulfonic Example 1 In a flask was placed 115.8 g. of

CH3 K)Z IO]IIZI5[OiliiCHzCHCHzNH:l CH3 CH3 CH3 2 and 230 ml. of benzene. The mixture was refluxed for two hours to drive moisture from the system. The mixture was cooled to 27 C. and 24.4 g. of 3-hydroxy-1- propane sulfonic acid sultone was added over a period of one minute. The reaction was somewhat exothermic. The reaction product was stripped to 140 C. at 2.0 mm. pressure to remove the benzene. The residue had the following structure:

CH3 CH3 [(CH )zSiO]l1.5[01/2 iCHzCHCHzIGCHgCHzCHzSOaE]:

CH CH Example 2 In a flask was placed 111.2 g. of

(CH O Si(CH NHCH CH NH and 230 ml. of benzene. This was refluxed for One hour at 85-86 C. to remove moisture. The reaction mixture was cooled to 31 C., and 61.1 g. of 3-hydroxy-1-propane sulfonic acid sultone was added. Within two minutes the reaction temperature had increased to 48 C.

The product was stripped to 144 C. at 18 mm. pressure to remove the solvent. A product of the following structure was obtained:

Example 3 In a flask was placed 13.6 g. of a polymer of the units CH3 OSIICHQCHCOH 5.5 g. of sodium methoxide, and 77.7 g. of methanol. An exothermic reaction resulted.

To this mixture was added 12.2. g. of 3-hydroxy-l-propane sulfonic acid sultone, and the reaction mixture was refluxed at 65.5 C. for two hours.

The methanol was evaporated from the solution, and the product isolated. 25.8 of

I (OSiCHgCHCOCHzCH CH SO;Na),,

was obtained as an amorphous solid.

Example 4 p In a 500 ml. flask was placed 20.1 g. of

77.7 g. of methanol, and 5.5 g. of sodium methoxide. The mixture was warmed in a range of 26.5 to 32 C. while an exothermic reaction took place, completely reacting the sodium methoxide.

Then 12.4 g. of 3-hydroxy-1-propane sulfonic acid sultone was added, and the reaction mixture was refluxed at 66.5 C. for 2 hours.

A pink, solid product was obtained on removing the methanol.

The product was believed to be 0 CHgOHzCHzSOsNQ.

(311: O CH2CH2CHzSi A7113 2 Example 5 In a 500 ml. flask was placed 27.8 g. of

(CH O) Si(CH NHCH CH NH and 45.9 g. of 3-hydroxy-1-propane sulfonic acid sultone was added over a 30 second period. The temperature of the reaction mixture rose from 28 C. to 94 C. without outside heating. On cooling, a hydroscopic solid was isolated with a formula:

(cmonsiwHmtfoHiomN(OHQCH OHgSOgH);

w CH CI'IqSOaH Example 6 In a 500 ml. flask was placed 19.6 g. of CH O) 3SICH2CH3SH 100 ml. of methanol, and 5.49 g. of sodium methoxide. The temperature of the reaction mixture rose slightly, indicating the formation of (CH O) SiCH CH SNa.

12.2 g. of 3-hydroxy-1-pr0pane sulfonic acid sultone was added to the mixture at 31 C. The temperature rose to 44 C. The mixture was refluxed at 64.5 C. for three hours.

A white, solid precipitate was recovered on cooling that was believed to be CH O) SiCH CH SCH CH CH SO Na Example 7 When 300 g. of

C5 15 $10) (OSl[CH2CHCHzCH3OH]2)1O I CF3 OH, CH3

Example 8 CH3 0 (CH OSlOMDKOSiHOCH[ NHg]z)z0 is mixed with 12.4 g. of

CsH11CH-CH1 O a i7CSO2 the following product is obtained: is reacted with 2.5 g. of 3-hyd1'oXy-1-propane sulfonic C8111, acid sultone, the following product is obtained: 1 6 (OHaOSiOa z) OSQiCHOCH O-lTICHaC8EESOaH 5 CsHn 2 20 Example 9 omsosNno noHioHisosn When 50 g. of 10 (CHaSiOm) oms i-omr m-r sr H (l) 013 CHQSO NHOHZOH CH SOBH (ILHzC-NH (3H2 -OSiCH:CH CH! CHaOCHa 3 CH3OCHflCHZO-"si l/2 gH CHzCNH OH OCH 0 3 Example 12v CFa 10 When 10 g. of

are reacted with 5 g. of 3-hydroxy-1-propane sulfonic acid sultone, the following product is obtained:

[I 00-0113): CH CHzCNCHqCHgOHzSO H l i l SiCHa CHzSOzNH OH; I -os1o11,o11 O omoomomo-sro on t 011 1 CH3 Exam le 10 v p is reacted with 3.1 g. of 3-hydroxy-1 propane sulfomc When 50 Of acid sultone, the following product is obtained:

(H) (30 a CHaC-O\ (I) /Si0 (osiomo CHzCHCHzCH2SOaNH4)50 4O (CH3)2C:NO 50 SOsNHi (CG-CH3): CH

B are reacted with 20 g. of a SlCH2 CHzSOzNCHzCHzCHgSOaH 02H! CHz-CH O CHa l 1 /O N:C\ CHz S0z CH3 the following product is obtained:

(N) (30 13 CHsCO (I) C2H5 /s1o (-OSiCHzOCH2OHCHzGHzSOaCHOHzCHzSOaNHOm (0H3)2o=No SO3(]]HCH2CH2SO3NH4 CzHa Example 11 Example 13 When 10g. of When 12 g. of

()0 NHCHaOHzGHgCHzNB:

SlCH2CH=0HCH2CH NCH2CHNH I CHgSOzNHz CH3 I CH3 (cmsiom) 01/2S[i-CH CF-OF 02115 o om omsomn, ONZC E CHzOCHa 3 and 6 g. of 3-hydroxy-1 propane sulfonic acid sultone are reacted, the following. product is obtained:

CHzCHzCHnSOaH SiCH2CH=CHCHzCHz S NCHzCH-NCHzOHgCHzSOaH is reacted with 9.6 g. of 3-hydroXy-1 propane sulfonic acid sultone, the following product is obtained:

(OH3) SiOHzCH OHOHzOOCHzOHzCH:

SO: L =oOCHgCH;CH SO3Ca Example 15 A. 2 g. of

OH; H,, CH

[(CHa)gSiOhLsIOrlgiCHzAHCHqN-CH CHgCHgS03H]:

were dissolved in 98 g. of CH OH. A 5 inch by 7 inch square of nylon fabric was dipped in this solution and dried in the air.

B. 2 g. of

(CH O) siCH CH cH NHCl-l CH NHCH CH CH SO H Example 16 When polyacrylic, polyolefin, and polyester fabrics are immersed in a solution of from 0.25 to 30 weight percent of one or more of the compositions disclosed in Examples .1 through where M is hydrogen, and from 99.75 to 70 weight percent of a volatile solvent that does not react with the fabric or the solute to be used and the fabrics are dried, said fabrics have a reduced tendency to acquire a static electricity charge.

Suitable solvents for this use are, among others, water, methanol, ethanol, isopropanol, hexane, cyclohexane, octane, decane, benzene, toluene, acetone, diethylether, etc.

In cases where siloxanes are employed the mol percent of the sulfonate-containing siloxane units must be sulficiently high to impart an antistat efiect to fabrics.

That which is claimed is:

1. A composition of the formula where R is selected from the group consisting of divalent and trivalent hydrocarbon, halohydrocarbon, and hydrocarbon ether radicals,

Y is selected from the group consisting of R is independently selected from the group consisting of hydrogen and aliphatic hydrocarbon radicals of 1 through 6 carbon atoms,

Q is an alkylene radical, of 2 through 4 carbon atoms that separates the two N groups by at least two carbon atoms, and

d is an integer of 0 through 1,

R is an alkylene radical that separates Y and by three carbon atoms,

M is selected from the group consisting of hydrogen, the ammonium radical and metal atoms selected from the group consisting of sodium, potassium, calcium and magnesium atoms,

0 is an integer of 1 through 3,

b is an integer of 1 through 2,

a is an integer of 1 through 2,

f is the reciprocal of the valence of M,

Z is selected from the group consisting of hydrogen atoms and monovalent hydrocarbon, halohydrocarbon, alkoxy, B-alkoxyalkoxy, phenoxy, acyloxy, and hydrocarbyl-substituted isocyanoxy radicals, and

e is an integer of 2 through 3, the sum of e+a being 4.

2.. A siloxane with at least one unit of the formula where R is selected from the group consisting of divalent and trivalent hydrocarbon, halohydrocarbon, and hydrocarbon ether radicals, Y is selected from the group consisting of where each R" is independently selected from the group consisting of hydrogen and aliphatic hydrocarbon radicals of 1 through 6 carbon atoms,

Q is an alkylene radical, of 2 through 4 carbon atoms that separates the two N groups by at least two carbon atoms, and

d is an integer of 0 through 1,

R is an alkylene radical that separates Y and S0 by three carbon atoms,

M is selected from the group consisting of hydrogen, the ammonium radical and metal atoms selected from the group consisting of sodium, potassium, calcium and magnesium atoms,

0 is an integer of 1 through 3,

b is an integer of 1 through 2,

a is an integer of 1 through 2,

f is the reciprocal of the valence of M,

Z is selected from the group consisting of hydrogen atoms and monovalent hydrocarbon, halohydrocarbon, alkoxy, fi-alkoxyalkoxy, phenoxy, acyloxy, and hydrocarbyl-substituted isocyanoxy radicals, and

e is an integer of 0 through 2, any other units in the siloxane being of the formula A SiO Where g is an integerwith a value of 0 through 3, and

A is selected from the group consisting of hydrogen,

rnonovalent hydrocarbon and halohydrocarbon radicals, alkoxy, ,B-alkoxyalkoxy, acyloxy, phenoxy, 11ydrocarbyl-substituted isocyanoxy, and hydroxy radicals.

(C11 0)3Si(OH2)aN(CH )zN(CHa)aSO3H 4. A siloxane of the average formula:

CH3 [(CH3) 8101115(OmSiCHzOHOHZNCHZOHZCH SO HM- CH3 CH3 CH3 t2. 5. A silane of claim 1 Where Y is 6. A siloxane of claim 2 where Y'is --NCH2CH2N- 7. A silane of claim 1 where Y is CH L 8. A siloxane of claim 2 where Y is References Cited UNITED STATES PATENTS 3,010,849 11/1961 Lense 117139.5 3,063,870 11/1962 Wakeman et a1. 117-139.5 3,109,012 10/1963 Rossmy et a1 260-4482 3,141,898 7/1964 Tiers 260-4482 3,187,033 6/ 1 965 Nitzschc eta1. 260-448.2 3,215,718 11/1965 Ryan 260--448.2

TOBIAS E. LEVOW, Primary Examiner. J. G. LEVITT, P. F. SHAVER, Assistant Examiners. 

1. A COMPOSITION OF THE FORMULA 